Method of reactivation of raney nickel

ABSTRACT

A poisoned Raney nickel catalyst from the hydrogenolysis of an organic peroxide polymer is reactivated by treating the catalyst with a 0.1-5 N solution of an activating reagent selected from the group consisting of ammonia, and an alkali metal or an alkaline earth metal hydroxide, carbonate or carboxylate having 1-4 carbon atoms at 20*-200*C under an inert gas atmosphere.

United States Patent [191 It/labuchi et al.

[ July 22, 1975 METHOD OF REACTIVATION OF RANEY NICKEL inventors:Shunsuke Mabuchi; Kenji Tsuzuki;

Ilideaki Matsunaga; Sadami Shimizu; Makoto Sun'lita, all of Shin-Nanyo,Japan Toyo Soda Manufacturing Co., Ltd,, Japan Filed: Dec. 26, 1973Appl. No.: 427,683

Assignee:

Foreign Application Priority Data Dec. 25, 1972 Japan 47-129219 U.S Cl,252/412; 252/414; 252/477 Q; 260/635 R Int. Cl BOlj 11/30 Field ofSearch 252/412, 414, 477 Q; 260/635 R References Cited UNITED STATESPATENTS 7/1952 Reynolds et a1. 252/412 2,879,306 3/1959 Hutchinson260/635 R 2,950,260 8/1960 Rosenbaum 252/412 3,544,485 12/1970 Taira etal. 252/477 0 FOREIGNPATENTS OR APPLICATIONS 833,592 4/1960 UnitedKingdom 252/412 44-9459 1/1969 Japan 252 477 0 Primary Examiner-WinstonA. Douglas Assistant Examiner-P. E. Konopko Attorney, Agent, orFirm-Oblon, Fisher. Spivak, McClelland & Maier [5 7 ABSTRACT 10 Claims,No Drawings 1. METHOD OF REACTIVATION or ANEY NICKEL BACKGROUND OF THEINVENTION 1. Field of the Invention: I j The present invention relatesto a method for reactivating poisoned Raney nickelwhich has been usedfor the hydrogenolysis of organic peroxide polymers.

SUMMARY OF THE INVENTION Accordingly, one object of the presentinvention is to provide a method for reactivating poisoned Raney nickelcatalysts.

Briefly, this object and other objects of the invention as.,hereinafterwill become more readily apparent can beattained by providing a methodfor the reactivation of a poisoned Raney nickel catalyst used for thehydrogenolysis of an organic peroxide polymer by treating the catalystwith a 0.1 N solution of an activating reagent selected from the groupconsisting of ammonia, an alkali metal or an alkaline earth'metalhydroxide, carbonate or carboxylate having 1-4 carbon atoms at 2 0-200Cunder an inert gas atmosphere.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS:

The poisoned Raney nickel catalysts to which'the process of the presentinvention is applicable include Raney nickel catalyst which are modifiedby small amounts of copper, chromium, iron, or the like which are usedin the hydrogenolysis of organic peroxide polymers. The organic peroxidepolymers which are subjected to hydrogenolysis include peroxide polymersof olefins which include conjugated diolefins such as butadiene,isoprene, 2-ethyll 3-butadiene, 2 ,3-dimethyl-l ,3-butadiene,2,5-dimethyl-2,4- hexadiene, alkyl substituted conjugated diolefinsthereof; cyclo substituted conjugated diolefins such as cyclopentadiene,cyclohexadiene, dimethylfuran, furan; alkyl substituted cycle conjugateddiolefins, and indene and styrene.

It has been found that organic peroxide polymers can be subjected tohydrogenolysis in the presence of a contact between the catalyst and thepolymer,'-the catalyst is suspended in a medium and then exposed'to ahydrogen atmosphere whereby the hydrogen is absorbed. At the same timetheorganic peroxide polymer is added to the medium which of coursedilutes it, through a high pressure, small amount constant volume pump,at a rate the same or less than the rate of hydrogenolysis of thepolymer. In the hydrogenolysis reaction, however, poisoning materialssuch as organic acids, polymers and the like continue to be absorbed onthe surface of the catalyst which in turn decreases the amount of activesurface area of the catalyst and results in a rapid decrease in activityeven though the contact method improves the reaction. Thus, the amountof the organic peroxide polymer which can be hydrogenated perunitamountof the Raney nickel catalyst is limited and of course,- it is. consumedas the reaction proceeds.

An-investigation into the problem of the deactivation. of the catalysthas revealed thatRaney nickel catalysts poisoned by organic peroxidepolymers can ,be reactivated by treating the inactivated catalyst with asolution of an activating reagent such as ammonia, an alkali metal or analkaline earth metal hydroxide carbonate or carboxylate having l-4carbon atoms under an inert gas atmosphere after each hydrogenolyisreaction. This method of reactivation of a poisoned Raney nickelcatalyst which is presently used in the hydrogenolysis of organicperoxide polymers has heretofore been unknown. When the procedure isrepeatedly used to remove the poison from the catalyst, the catalyst canbe reused from 50 to 100 times.

In the reactivation of Raney nickel, the temperature at which thecatalyst is treated, the concentration of the activating reagent and thetreatment time all influence the degree of activation. The treatmenttemperature usually ranges from 20 to 200C, preferably 50 to 120C,especially 70 to 120C. If the treatment temperature is greater than 200Cthe aluminum component of the Raney nickel catalyst is dissolved andconsequently the nickel atoms are rearranged. Also, the

crystalline particles are increased and the catalytic activity isdecreased. From the viewpoint of catalyst life, it is preferably thatthe temperature be lower. However, at temperatures less than 20C, theseparation of the absorbed poison from the Raney nickel catalyst is tooslow and the treatment time is too long. Suitable media for theactivating reagents include water, and lower alcohols such as methanol,ethanol'and isopropanol. Satisfactory treatment results are alsoachieved when the concentration of the activating reagent Raney nickelcatalyst. However the organic peroxide hydrogenation reaction. In orderto improve the ranges from 0.1 to 5 N.

The treatment time depends upon the concentration of the activatingreagent, the treatment temperatures and the ratio of the organicperoxide polymer to the Raney nickel catalyst in the hydrogenolysisreaction and is usually 2 to 8 hours. The treatment conditions for theRaney nickel catalyst depend upon the ratio of the organic peroxidepolymer to the Raney nickel, which must be severe at increased ratios.From the viewpoint of catalyst life, severe treatment times arepreferably used rather than using increased treatment temperatures.Suitable inert gases which can be used in the treatment of the poisonedRaney nickel catalyst include hydrogen, nitrogen and the like. Thesegases do not adversely effect the activity of the catalyst, andpreferably hydrogen is used.

Having generally described this invention, a further understanding canbe obtained by reference to certain specific examples which are providedherein for pur posesof illustration only and are not intended to belimiting unless otherwise specified.

EXAMPLE 1 butanediol, 1.5 g of 2-methy1-3,4butanediol and 6.4 g 20 of2-methy1-1, 4-butanediol.

The total yield of the diols based on thej soprene peroxide polymer was45.7%. The poisoned Raney nickel catalyst and 100 cc of an aqueous 0.5N-NaOl-Isolution were charged into the 200 cc autoclave equipped with anelectromagnetic stirrer, and the mixture was heated and stirred at 90Cfor 3 hours under a hydrogen atmosphere to activate the catalyst. The.catalyst was sepa-.

rated, and thereafter wasused for the hydrogenolysis of the isopreneperoxide polymer. The operation was repeated 30 times with the samecatalyst, and no decrease inactivity of the catalyst was not found.

EXAMPLES 2 10 In the autoclave of Example 1, each of the peroxidepolymers shown in Table 1 were hydrogenated under the reactionconditions shown in Table 1. After each hydrogenolysis reaction, thepoisoned Raney nickel catalyst was treated under the conditions shown inTable 1. This cycle was repeated a number of times as shown in eachExample in the table. The results are shown in Table 1.

TABLE 1 Reaction Conditions Reactivation Product Conditions Repe- RanReacated Total Exey tion Reacuse of yield amnictempetion cata- Tempeofple Peroxide Polymer kel rature pressure lyst Alkali rature Diol diol(g) (m l (g) (C1 g/ (time) (C) (2) ('1') 2-methyl'- Z-methyl-Z-methylisoprene peroxide 1.2- 3, l polymer 10 60 5O 1 butanediolbutanediol butanediol 45.7 20 0.20 1.7 1.5 6.3 2 0.5N-Na CO;,

2,5-dimethyl-2,4- hexadiene peroxide I polymer 1 0.14 10 50 70 16063622,5-dimethyl-2,S-hexanediol 17.1 83.2 3 3N-ammonia 20 0.5 10 50 70 22100 cc 100 2,S-dimethyl-2,5-hexanediol 16.7 81.2

2.5-dimethy12,4- hexadiene peroxide polymer 4" 20 0.14 10 50 50 l2,5-dimethyl-2.5-hexanediol 17.0 82.7

0.1N-KOH aq sol. I i 20 0.14 10 50 50 100 cc 902,5-dimethyl-2,S-hexanediol 16.5 80

2,5-dimethy1-2,4- hexadiene peroxide polymer 5* 20 0.14 7 50 70 12,5-dimethyl-2,S-hexanediol 17.1 .832

0.5N-NaOH aq. s01. 20 0.14 7 50 7O 100 cc 90 2.5-dimethyl-2,S-hexanediol16.8 81.8

2 eth 1-l.3- Z-ethyl- Z-ethyl- 2-ethylbuta iene l 3 1 peroxide polymerbutanediol butanediol butanediol 6 20 0.18 10 60 1 1.9 1.1 5.6 72.9'0.5N-Ba(OH)-, aq. sol. 20 0.18 10 50 25 100 cc 100 1.7 v 1.0 5.5 69.5

2.3-dimethy1-L3- 2.3-dimethy1- 2,3-dimethy1- butadiene peroxide 1 1,2 14. polymer butanediol butanediol 7 20 0.18 10 60 1 3.7 6.5 86.4

. 0.2N-LiOH aq. sol 20 0.18 10 60 80 15 cc 3.6 6.4 84.7 cyclopentadieneperoxide polymer 8 2 0.20 10 5O 70 1 1,4-cyclopentanediol 15.5 74.5

4N-NaOH aq. 20 0.20 10 5O 70 40 sol. 100 cc 70 1,4-cyc1opentanediol 15.172.5

TABLE l-Contmued Reaction Conditions Reactivation Product ConditionsRepe- Ran- Reacated Tm l Exey tion Reacuse of i ld amnictempetion cata-Tempeof ple Peroxide Polymer kel rature pressure lyst Alkali rature Dioldiol (g) (mole) (g) 7 g/ m PC) (a) ('11 styrene peroxide polymer benzylphenyl- 9 20 10 40 20 l alcohol 1.3 glycol 16.3 88.6 0.5N-KOH ethanolbenzyl phenyl- 20 0.14 10 40 20 10 sol. 100 cc 90 alcohol 1.2 glycol15.7 85.0

styrene peroxide polymer benzyl phenyl- 10 20 0.14 10 40 20 1 alcohol1.3 glycol 16.2 88.1

lN-AcONa benzyl phenyl- 20 0.14 '10 40 20 50 sol. 100 cc 90 alcohol 1.2glycol 15.7 85.0

in Example 4. a modified Raney nickel catalyst containing 1% chromiumwas used. In-Example 5. thc treatment time was hours while in the otherExamples. the treatment time was 3 hours.

. EXAMPLE 1 l Into a 200 cc autoclave "equipped with an electromagneticstirrer, g of Raney nickel (manufactured 'by Kawaken Fine Chemical K.K.)and 50 g of ethyl acejtate were charged. Further,'a 60 g solution of0.23 mole butadiene peroxide polymer (as C H O in ethyl acetate wascharge into the autoclave at 70 C under a hydrogen pressure of '50 kg/cmover 2 hours. by a small, constant-amount injection pump. After thehydrogenolysis was completed, the catalyst was separated and thereaction mixture was analyzed by gas chromatography.

The reaction mixture contained 1 1.6 g of 1,4- butanediol, 3.82 g of1,2-butanediol'and 1.95 g of other diols.

Theyield of 1,4-butanediol based on the butadiene peroxide polymer was56%. The poisoned Raney nickel catalyst and 100 cc of an aqueous 0.5N-NaOH'solution were charged into the 200 cc autoclave equipped with anelectromagnetic stirrer, and the mixtu re was heated and stirred at 90Cfor 3 hours under a hydrogen atmosphere to activate the catalyst. Thecatalyst was separated and was used for the hydrogenolysis of isopreneperoxide polymer.

,The operation'was repeated 100 times using the same catalyst, and nodecrease in activity of the catalyst was found.

EXAMPLES 12-19 'was repeated for the number of times shown in the tablefor each Example. Th'e'results are shown in Table 40 TABLE 2 ReactionConditions Reactivation Product Conditions Exambutaper- Raney Reac-Reaction Repeated Tempe- 1,4- 1.2- Yield of pie diene oxide nickel tionpressure use of Alkali rature butanebutaneoth- 1,4-

poly- (mole) (g) tempecatalyst (C) diol diol er butanemer rature (kg/cm)(time) (g) (g) diol (g) (C) 20 0.23 10 90 10 1 11.59 3.80 1.95 56 120.3N-LiOH 20 0.23 10 90 10 aq. sol. 130 11.39 3.75 1.97 55 100 cc 200.23 10 300 1 11.58 3.86 1.91 56 13 20 0.23 10 50 300 70 4N-KOH 70 10.973.65 2.03 53 aq. sol. 100 cc 20 0.23 10 7O 50 1 11.59 3.82 1.93 56 140.5N-KOH 20 0.23 10 70 50 90 ethanol sol. 90 1 1.40 3.67 1.94 55 100 cc20 0.23 10* 50 l 11.60 3.83 1.92 56 15* 20 0.23 10* 70 50 8O 0.5N-Ba(OH)100 11.17 3.74 2.00 54 aq. sol. 100 cc 20 0.23 10 70 100 l 11.61 3.871.91 56 0.1N-NaOH 16* 20 0.23 10 70 100 20 aq. sol. 70 10.93 3.60 2.0453 100 cc 0.5N-NaOH 20 0.23 10 70 100 70 aq. sol. 90 11.41 3.80 1.98 55100 cc 20 0.23 10 90 50 l 11.58 3.83 1.96 56 17 20 0,23 10 5O 5O3N-amm0nia 100 l 1.41 3.79 2.01 55 100 cc 20 0.23 10 70 5O 1 11.60 3.821.97 56 18 20 0.23 10 70 50 6O O.5N-CH COONa aq. so]. 100 cc 11.40 3.772.00 55 TABLE 2 Continued Reaction Conditions Reactivation ProductConditions Exambutaper Raney Rcac- Reaction Repeated Tcmpe- 1. .2- Yieldof ple diene oxide nickel tion pressure use of Alkali raturebutanebutaneothl.4-

poly- (mole) (g) tempecatalyst (C) diol diol er butanemer rature(kg/cm") (time) I (g) (g) diol (g) 20 0.23 l 70 50 l I l L58 3.75 1.9856 19 ().5NK CO;,

20 0.23 It) 70 50 60 aq. sol. 90 ll.4l 3.80 I92 55 ln Example IS. amodified Rancy nickel catalyst containing l7: chromium was used. lnExample 16. the poisoned Rancy nickel was treated at 70C with (LlN-NaOHeach time after the reaction for 20 times. and thereafter was treated at90C with (l.5N NaOH thereafter.

Having now fully described this invention, it will be apparent to one ofordinary skill in the art that many changes and modifications can bemade thereto without departing from the spirit or scope of the inventionas set forth herein.

' What is claimed as new and intended to be covered by Letters Patentis:

1. A method for the reactivation of a poisoned Raney nickel catalystmodified by a small amount of metal from the group consisting of copper,chromium and iron which is used for. the hydrogenolysis of inorganicperoxide polymer to form a diol product which comprises treating saidcatalyst with a 0.1 N aqueous or lower alcohol solution of an activatingreagent selected from the group consisting of ammonia, an alkaline earthm etal. hydroxide.- carbonate or carboxylate having 1 4 carbon atoms'andan'alkali metal carbonate or carboxylate having from 1 4 carbon atoms at2020( )C underan atmosphere of hydrogen or nitrogen from 2 to 8 hours,and separating said treated catalyst from said aqueous or lower alcoholsolution.

2. The method of claim 1, wherein said organic peroxide polymer is aconjugated diolefin peroxide polymer, a cyclo substituted conjugateddiolefin peroxide polymer, an alkyl substituted cyclo conjugateddiolefin peroxide polymer, an indene peroxide polymer or a styreneperoxide polymer.

3. The method of claim 1, wherein said organic peroxide polymer isbutadiene peroxide polymer.

4. The method of claim 1, wherein the organic peroxide polymer is anolefin peroxide polymer of an olefin selected from the group consistingI, of isoprene, 2,5 dimethyl-2A-hexadiene; 2,3-dimethyl- 2,3-butadienecyclopentadiene and styrene. L Y

5. The method of claim 1, wherein said solution of the activatingreagent is prepared from water.

6. The'method of claim 1, wherein said activating reagent is an alkalimetal carbonate;

7.- The method of claim 1, wherein said activating reagent is an alkalimetal carboxylatehaving from 1 to 4 carbon atoms.

8. The method of claim 1, wherein said activating re agent is analkaline earth metal hydroxide.

9. The method of claim 1, wherein said activatingreagent is an alkalineearth metal carbonate. 10. The method of claim 1, wherein saidactivating reagent is an alkaline earth metal carboxylate having from 1to 4 carbon atoms.

I 2-ethyl-l ,3-butadiene,

r UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 23,896,051 DATED duty 22, 1975 |NvENTOR(S) Shunsuke Mabuchi et a] It iscertifi ed that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 7, Iine 26 (Claim 1, line 4) change "inorganic" to an organicSigned and Scaled this T t-f rth a I {SEAL} weny out D y 0f August 1976Arrest:

RUTH c. msoN I c. MARSHALL DANN Anestmg Officer Commissioner nj'latemsand Trademarks

1. A METHOD FOR THE REACTIVATION OF POISONED RANEY NICKE CATALYSTMODIFIED BY A SMALL AMOUNT OF METAL FROM THE GROUP CONSISTING OF COPPER,CHROMIUM AND IRON WHICH IS USED FOR THE HYDROGENOLYSIS OF INORGANICPEROXIDE POLYMER TO FORM A DIOL PRODUCT WHICH COMPRISES TREATING SAIDCATALYST WITH A 0.1 - 5 N AQUEOUS OR LOWER ALCOHOL SOLUTION OF ANACTIVATING REAGENT SELECTED FROM THE GROUP CONSISTING OF AMMONIA, ANALKALINE EARTH HYDROXIDE, CARBONATE OR CARBOXYLATE HAVING 1 -4 CARBONATOMS AND AN ALKALI METAL CARBONATE OR CARBOXYLATE HAVING FROM 1 - 4CARBON ATOMS AT 20*-200*C UNDER AN ATMOSPHERE OF HYDROGEN OR NITROGENFROM 2 TO 8 HOURS, AND SEPARATING SAID TREATED CATALYST FROM SAIDAQUEOUS OR LOWER ALCOHOL SOLUTION.
 2. The method of claim 1, whereinsaid organic peroxide polymer is a conjugated diolefin peroxide polymer,a cyclo substituted conjugated diolefin peroxide polymer, an alkylsubstituted cyclo conjugated diolefin peroxide polymer, an indeneperoxide polymer or a styrenE peroxide polymer.
 3. The method of claim1, wherein said organic peroxide polymer is butadiene peroxide polymer.4. The method of claim 1, wherein the organic peroxide polymer is anolefin peroxide polymer of an olefin selected from the group consistingof isoprene, 2,5-dimethyl-2,4-hexadiene, 2-ethyl-1,3-butadiene,2,3-dimethyl-2,3-butadiene cyclopentadiene and styrene.
 5. The method ofclaim 1, wherein said solution of the activating reagent is preparedfrom water.
 6. The method of claim 1, wherein said activating reagent isan alkali metal carbonate.
 7. The method of claim 1, wherein saidactivating reagent is an alkali metal carboxylate having from 1 to 4carbon atoms.
 8. The method of claim 1, wherein said activating reagentis an alkaline earth metal hydroxide.
 9. The method of claim 1, whereinsaid activating reagent is an alkaline earth metal carbonate.
 10. Themethod of claim 1, wherein said activating reagent is an alkaline earthmetal carboxylate having from 1 to 4 carbon atoms.